Shifted indophenol dye developers

ABSTRACT

Dye developers and processes for making said dye developers are disclosed, along with photographic compositions and photographic elements containing said dye developers wherein the dye developer comprises a silver halide developing moiety connected to an indophenol moiety. In one aspect, the light-absorption characteristics of dye developers comprising the indophenol moiety when incorporated in a photographic element can be shifted to provide for exposure of a photosensitive material without substantial absorption competition and then can be shifted by contact with an &#39;&#39;onium compound to provide a good image dye. In another aspect, photographic elements are disclosed which contain a photosensitive composition having associated therewith a shifted indophenol dye developer; preferably, the photographic elements are used in image transfer film units.

[4 Dec. 17, 1974 SHIFTED INDOPHENOL DYE DEVELOPERS [75] Inventors:Walter Monroe Bush, Victor; Daniel Francis Reardon, Rochester, both ofNY.

[73] Assignee: Eastman Kodak Company,

Rochester, NY.

22 Filedz Feb. 17, 1972 21 Appl. No.: 227,113

[52] US. Cl 96/29 D, 96/3, 96/77,

[51] Int. Cl. G036 7/00, G03c 5/54, G03c 1/40,

[58] Field of Search 96/29 D, 99, 3, 77

[56] References Cited UNITED STATES PATENTS 3,239,336 3/1966 Rogers etal 96/3 3,255,001 6/1966 Blout et al. 96/29 D 3,537,850. 11/1970 Simon6/29 D 3,698,897 10/1972 Gompf et al 96/29 D 3,725,062 4/1973 Andersonet al. 96/3 3,728,113 4/1973 Becker et a1 96/3 3,765,886 10/1973 Bush eta1. 96/77 2/1974 Bush et al. 1.96/22 Primary E.\aminerNorman G. TorchinAssistant Examiner-Richard L. Schilling Attorney, Agent, or Firm-G. E.Battist 5 7] ABSTRACT Dye developers and processes for making said dyedevelopers are disclosed, along with photographic compositions andphotographic elements containing said dye developers wherein the dyedeveloper comprises a silver halide developing moiety connected to anindophenol moiety. In one aspect, the light-absorption characteristicsof dye developers comprising the indophenol moiety when incorporated ina photographic element can be shifted to provide for exposure of aphotosensitive material without substantial absorption competition andthen can be shifted by contact with an onium compound to provide a goodimage dye. In another aspect, photographic elements are disclosed whichcontain a photosensitive composition having associated therewith ashifted indophenol dye developer;

image transfer film units.

' 39 Claims, 6 Drawing Figures PATENTEL EU) I (i974 sum 1 0s 2 M ED N QR

1 SHIFTED INDOPHENOL DYE DEVELOPERS This invention relates tocompositions of matter, processes for preparing compositions of matter,photographic elements containing these compositions of matter andprocesses for forming photographic image records. In one aspect, thisinvention relates to shifted dye developers wherein the dye is anindophenol moiety. In another aspect, this invention relates tophotographic elements for recording an imagewise exposure, whichelements contain shifted indophenol dye developers and to photographicimage records containing a dye developer wherein the dye is an oniumindophenoxide. In still another aspect, this invention relates toimproved image transfer film units and processes for forming imagerecords in image transfer film units.

It is known in the prior art to use dye developers in photographicelements such as image transfer systems as disclosed in U.S. Pat. Nos.2,983,606, 3,225,001, etc., where most of the dyes of said dyedevelopers are anthraquinone dyes or azo dyes. It is also known in theart to use shifted dye developers in image transfer systems such asdisclosed in U.S. Pat. No. 3,336,287 issuedAug. 15, 1967, 3,307,947issued Mar. 7, 1967, and the like. Several references also disclose theuse of hydrolyzable groups attached to an anthraquinone or azo dye toshift the color of the dye temporarily toward lower wavelengths wherebytheir use in a photosensitive element will result in a reducedabsorption of light available for exposure of the associated silverhalide emulsion or an inner silver halide emulsion with respect to thedirection of exposure U.S. Pat. Nos. 3,230,082 issued Jan. 18, 1966,3,230,085 issued Jan. 18, I966, 3,146,102 (column 12) by Wey erts et a1issued Aug. 25, 1964, etc. However, improved classes of dye developersare desired which would substantially obviate the absorption competitionwith the associated photosensitive emulsion and underlyingphotosensitive emulsion layers and at the same time provide short imagetransfer times and good image quality in the image record aftertransfer. r

We have now discovered a new class of compounds which can be used inphotographic elements, and especially in image transfer film units, toprovide improved transfer systems and improved image properties.Generally, the compounds are dye developers wherein the dye is anindophenol, referred to herein as a shifted indophenol dye developer.These compounds can be coated in the photosensitive element with lowcolor absorption, and after exposure of the photosensitive element canbe brought into contact with a positively charged compound which ispreferably an onium com-. pound to produce an image dye having very goodimage characteristics including stability, density and the like.

In one preferred embodiment, this invention relates to a photographicelement comprising a support and at least one layer thereon containing aphotosensitive, image-recordng material having associated therewith adye developer of the general formula:

D-(SID) wherein D-is an aromatic group which is a silver halidedeveloper and (SID) is an indophenol dye moiety.

In another embodiment, this invention relates-to an image transfer filmunit comprising a photosensitive element containing a blue-sensitivesilver halide emulsion layer having associated therewith ayellow-forming indophenol dye developer, a green-sensitive silver halideemulsion layer having associated therewith a magenta-forming indophenoldye developer, and a redsensitive silver halide emulsion havingassociated therewith a cyan-forming indophenol dye developer.

In another embodiment, this invention relates to a photographic filmunit comprising:

1. a photosensitive element comprising a support having thereon a layercontaining a silver halide composition having associated therewith a dyedeveloper having the formula:

D-(SID) wherein D-is a silver halide developing group, either in theoxidized or unoxidized state, (SID) is an indophenol moiety, and M is anonium group.

In another highly preferred embodiment, this invention relates to imagetransfer elements comprising the combination of a shifted indophenol dyedeveloper and an incorporated auxiliary silver halide developer which isa reducing agent.

In the drawings, FIG. 1 shows a representative .absorption shift whichis obtained with a yellow indophenol based on an open-chainketomethylene coupler (line Y), a magenta indophenol based on apyrazolone color coupler (line M), and a cyan indophenol based on aphenolic color coupler (line C), wherein the absorption characteristicsof the indophenols as incorporated in the photographic element areshown, respectively, as lines SY, SM and SC and the absorptioncharacteristics after contact with an onium compound are shown as linesY, M and C. Further details of the absorption shift are described inBush et al, U.S. Ser. No. 169,706 filed Aug. 6, 1971, now U.S. Pat. No.3,791,827, which is incorporated herein by reference. FIGS. 2 and 3 showrepresentative absorption characteristics of the dye developers ofExamples 2 (Com pound I) and 8 (Compound IV).

In FIGS. 4-6, a preferred film unit is described which is based on theshifted indophenol dye developers.

The shifted dye developers of this invention are generally those whichcomprise a silver halide developing agent moiety linked to an indophenoldye moiety. Generally, the shifted dye developers can be represented bythe formula:

D-(SID) wherein D-is a moiety of a silver halide developing agentincluding those having hydrolyzable groups thereon, and preferably is adisubstituted aromatic group such as a naphthalene or, more preferably,a phenylene group wherein the disubstituted groups are hydroxy groups,primary amino groups or alkylamino 2,369,489 by Porter et a1 issued Feb.

groups, including substituted alkylamino groups, wherein the secondsubstituent is preferably in the ortho or para position; and (SID) is ashifted indophenol dye moiety including, of course, the desired linkinggroups between the dye moiety and the developing agent moiety,especially where chromophore insulating groups are desired. In onepreferred embodiment, (SID) can be represented by the formula:

(COUP)=N-Ar-OH wherein Aris an arylene group comprising from 6 to 20carbon atoms including substituted and unsubstituted arylene groups,fused-ring substituents and the like, and is preferably a phenylenegroup which is preferably substituted with halogen atoms or groupscontaining halogen atoms in the ortho or meta positions of the ring; and(COUP) is a color-forming coupler including the linking group to D-,suchas phenolic couplers, pyrazolone couplers, pyrazolotriazolecouplers, couplers having openchain methylene groups and the like,wherein said coupler is linked to said nitrogen atom through a carbonatom at the coupling position. Generally, when the above shifted dyedevelopers are utilized in an image transfer film unit, the shifted dyedeveloper is diffusible and will migrate to an image-receiving layerupon contact with an alkaline processing solution unless the developergroup is oxidized by reaction with developable silver halide or oxidizedwith a redox agent; the image-receiving layer preferably has an oniumcompound associated therewith to provide the onium indophenoxide imagedye.

The compounds or groups referred to herein as couplers contain acoupling position which is generally known to those skilled in the artas being the position on the coupler molecule that reacts or coupleswith oxidized color developing agents. Typical useful couplers includephenolic couplers, including a-naphthols which couple at the 4-position,open-chain ketomethylene couplers which couple at the carbon atomforming the methylene moiety (e.g.,

wherein denotes the coupling position),5-pyrazolone couplers whichcouple at the carbon atom in the 4- position, and the like. Typicalspecific coupler compounds which can be reacted with p-aminophenols toform the indophenol moiety according to this invention are disclosed inUS. Pat. Nos. 2,407,210 by Weissberger et al issued Sept. 3, 1946;2,298,443 by Weissberger issued Oct. 13, 1942; 2,875,057 by McCrossen eta1 issued Feb. 24, 1959; 3,265,506 by Weissberger et a1 issued Aug. 9,1966; 3,408,194 by Loria Issued Oct. 29, 1968; 3,447,928 by Loria issuedJune 3, 1969; 13, 1945; 2,600,788 by Loria et a1 issued June 17, 1952;2,908,573 by Bush et al issued Oct. '13, 1959; 3,062,653 by Weissbergeret a1 issued Nov. 6, 1962; 3,419,391 by Young issued Dec. 31, 1968",3,519,429 by Lestina issued July 7, 1970; 3,152,896 by Tuite issu'edOct. 13, 1964; 2,423,730 by Salminen et :11 issued July 8, 1947;2,474,293 by Weissberger et a1 issued June 28, 1949; 3,476,563 by Loriaissued Nov. 4, 1969; 2,772,162 by Salminen et a1 issued Nov. 27, 1956;and 3,002,836 by Vittum et a1 issued Oct. 3, 1961; and US.

Ser. No. 778,333 by Bailey et al filed Nov. 22, 1968, now abandoned;which are all incorporated herein by reference.

The group defined as Ar above is preferably the residue of an aromaticcolor developing agent such as an aminophenol, a phenyle'nediamine andthe like and, of course, including the various substituents on thearomatic group which are known in the art for the respective colordeveloping agent. In one preferred embodiment where Ar is the nucleus ofan'aminophenol developing agent, the aromatic compound can contain thesubstituents as disclosed, for example, in Bush et al, US. Ser. No.169,706 filed Aug. 6, 1971 now US. Pat. No. 3,791,827, which isincorporated herein by reference.

In the shifted indophenol dye developers, the indophenol moietypreferably contains an insulating linkage connecting it to thedeveloping agent moiety (D-). Insulating linkages of this type,sometimes referred to as achromophoric groups or bonds, are known in theart, for example, as disclosed in US. Pat. No. 3,255,001 issued June 7,1966. The insulating group does not contribute a color-producing groupto the indophenol dye chromophore, but acts to prevent or. interrupt anysystem of conjugation or resonance extending from the azomethine groupsof the indophenol moiety to the developing group, i.e., such as ahydroquinone group. Thus, any influence of the developer group on thecolor characteristics of the azomethine linkage is substantiallyexcluded. The insulating linkage which preferably forms a part of theindophenol moiety as defined herein can be any group which will break upthe resonance system, for example, those groups listed in US. Pat. No.3,255,001 issued June 7, 1966, and the like.

The term azomethine linkage" as used herein is understood to mean thegrouping:

' (COUP)=N--ArOH wherein (COUP) is a color coupler such as a pyrazolonecolor coupler, a pyrazolotriazole coupler, an open-chain ketomethylenecolor coupler, a phenolic color coupler and the like, which is connectedto the nitrogen atom in the coupling position of said coupler; and Ar isas defined above.

The term nondiffusing used herein has the meaning commonly applied tothe term in color photography and denotes materials which for allpractical purposes do not migrate or wander through organic colloidlayers, such as gelatin, comprising the sensitive elements of theinvention. The same meaning is to be attached to the term immobile.

The term diffusible as applied to the colorproviding materials of thisinvention has the converse meaning and denotes materials having theproperty of diffusing effectively through the colloid layers of thesensitive elements in the presence of the nondiffusing materials. Mobilehas the same-meaning.

The shifted indophenols are reacted with onium salts at appropriatetimes in photographic processes to pro vide a bathochromic absorptionshift, thus forming an onium indophenoxide. The onium indophenoxides cangenerally be represented by the formula:

D-(SID) M and more preferably by:

D-(COUP)=N-Ar 'M wherein D-, (SID), (COUP) and Ar are as defined above,and M is an onium group including sulfonium, phosphonium and,preferably, quaternary ammonium groups. When the onium indophenoxide isformed in or has transferred to the desired imagereceiving layer, thedeveloper group can be in the oxidized or unoxidized state.

The onium salts used to form the onium indophenoxides are generallyquaternary ammonium salts, quaternary phosphonium salts, tertiarysulfonium salts and the like, and are generally used in concentrationsnecessary to form an onium indophenoxide with all of the indophenolpresent in the photographic element. When the onium compound is immobileor ballasted and present in an image layer, it is generally utilized inconcentrations of about 25 mg. to about 1,000 mg. per square foot, andpreferably about 50 to about 500 mg. per square foot, depending, ofcourse, on the ratio of onium atoms to molecular weight of the compoundemployed. When the onium salt is supplied by a solution such as in theprocessing solution, typical useful concentrations range from 0.01% byweight to about by weight of the onium compound to provide completereaction, again depending on the concentration of the dye in thephotographic element and the ratio of onium groups to molecular weightof the oniumcompound.

In one embodiment of this invention, color image transfer systems areprepared by using an appropriate shifted indophenol dye in each of threedifferently sensitized emulsion layers of a photographic element.

One layer of the element comprises a blue-sensitive silver halideemulsion which has associated therewith a shifted yellow indophenol dyedeveloper. Typical shifted yellow dye developers have the formula:

wherein D-and Ar are as defined above and (KMC) is an open-chainketomethylene color coupler connected to said nitrogen atom at itscoupling position. A typical Another layer of the element comprises agreensensitive silver halide emulsion having associated therewith ashifted magenta indophenol dye developer. Typical shifted magenta dyedevelopers have the formula:

wherein D-and Ar are as defined above and PYZ is a pyrazolone orpyrazolotriazole color coupler, and

preferably a color couplerwhich contains either the moieties:

-CH2 C 0 NH- and Compound V wherein D-and Ar are as defined above andPhC is a phenolic color coupler connected to said nitrogen atom at itscoupling position. Typical specific compounds of this type are:

Compound Ill l l CHzCONH and ll (1)11 0 u 1-Nnc o can,

*(ClhhilNII-Y N I V l o it Compound IV The shifted indophenol dyedevelopers can be prepared by several techniques. In one embodiment,oxichromic developers are prepared as described in Lestina and Bush,U.S. Ser. No. 206,949 entitled Oxichromic Compounds, StabilizedOxichromic Compounds and Processes for Preparing Same filed Dec. 10,1971, and the oxichromic developers are then chromogenically oxidized byaerial oxidation, electrochemical oxidation and the like to provideindophenol-dye developers. in another embodiment, the indophenol dyedevel opers are prepared by l) reacting a masked silver halidedeveloping compound with a color coupler by a condensation reaction, 2)reacting the condensation product with an aminophenol and 3) thenremoving the masking groups from the moiety which was the silver halidedeveloping compound. in certain variations, the aminophenol can bereacted with the color coupler before condensation with the maskedsilver halide developing compound. The color coupler can be reacted withan oxidized aminophenol to form the dye or, in certain embodiments, thecouplers when halogenated on the active methylene group can be reactedwith unoxidized 'aminophenols as disclosed in U.S. Ser. Nos. 206,924 byMachiele or 206,927, now abandoned, by Reardon, both filed Dec. 10,1971.

Generally, it is known in the'prior art to make dye developers byreacting a'masked developer with a dye moiety by a condensationreaction, for example, as disclosed in Journal of Chemical andEngineering Data, Vol. 9, No. 2, 1964, pp. 232-238. After condensation,the masking groups protecting the silver halide developing functions canbe readily removed since dyes used in the past, such as azo dyes,anthraquinone dyes and the like, are relatively stable to conditionsnecessary to remove the masking groups. In one embodiment, we have nowfound that dye developers comprising dye moieties containing anazomethine linkage, such as indophenol dyes, can be prepared bycondensation reactions with masked developers when precautions are takento use mild hydrolysis conditions wherein the pH is maintained betweenpH of about 7 to about 10 and the masking groups are groups which willreadily hydrolyze under these conditions such as, for example, maskinggroups forming carbonates, oxalates, trifluoroacetates and thelike withthe silver halide developing moiety. When masking groups such as acetoxygroups are used on the silver halide developing moiety, hydrolysis ofthe masking group is generally accompanied by substantial destruction ofthe indophenol. I

The hydrolysis reaction is preferably carried out with a mildhydrolyzing agent such as weak alkali, methylamine, thiourea, zinc andacetic acid and the like. Generally, the hydrolysis procedure isdependent on the groups on the dye moiety and the specific group to beremoved. However, the above hydrolyzing agents can generally be used toachieve removal of carbonate, oxalate, trifluoroacetate groups and thelike.

In certain preparations of the dye developers of this invention, themasking groups are attached to a developing moiety which is preferably apolyhydroxybenzene compound such as hydroquinone', and the maskinggroups are carbonate-containing masking groups such as carboalkoxygroups, carbobenzoxy groups and the like which can contain from 2-20carbon atoms.

The shifted indophenol dye developers are especially useful in imagetransfer systems since they can be incorporated in the silver halideimage-recording layer without substantial detrimental adsorption oflight in any of the recording layers, i.e.-, the yellow, green and redrecording layers, During development, the indophenol dye developers areinsolubilized in those areas where silver halide developmentoccurs andthe unreacted indophenol dye developer is free to diffuse or migrate toa receiver layer such as a mordant layer. At some point after imagewiseexposure of the silver .halide layer, the indophenol dye developer canbe contacted with an onium compound to convert the indophenol moiety toanonium indophenoxide which will provide a desired shift in coloradsorption providing highly useful dyes for color systems.

A particularly preferred embodiment of the present invention involves aphotographic film unit comprising:

1. a photosensitive element comprising a support having thereon a silverhalide emulsion layer having associated therewith an indophenol dyedeveloper,

2. a dye image-receiving layer having associated therewith an oniumcompound, and

3. a container means for discharging an alkaline processing compositionwithin said unit. Preferably, said container means is a rupturablecontainer which is positioned during processing of said film unit sothat a compressive force applied to the container by pressure-applyingmembers will effect a discharge of the containers contents into the filmunit. I

The dye image-receiving layer of the film unit can be located on aseparate support adapted to be superposed on the photosensitive elementafter exposure thereof.

Such image-receiving elements are disclosed, for example, in U.S. Pat.No. 3,362,819. The rupturable container is usually positioned duringprocessing of said film unit so that a compressive force applied to thecontainer by pressure-applying members in a camera will effect adischarge of the containers contents between the image-receiving elementand the outermost layer of the photosensitive element. The dyeimage-receiving layer can also be located integral with thephotosensitive element between the support and the lowermostphotosensitive silver halide emulsion layer. Such integralreceiver-negative photosensitive elements are disclosed, for example, inU.S. Pat. No. 3,415,644 and are useful in camera apparatus of the typedisclosed in Belgian pat. Nos. 718,553 and 718,554. The processingcomposition for such integral elements wherein the receiver ispermanently laminated to the negative contains opacifying agents such astitanium dioxide or carbon black. Barrier layers such as those describedin subsequent paragraphsmay be usedto advantage in such integralelements between the various emulsion and dye-developer layers.

In one highly preferred embodiment according to this invention, which isshown in FIG. in detail, the shifted indophenol dye developers are usedin an integral image transfer system wherein the image-receiving layeris separated from the image-recording layers, i.e., photosensitivelayers containing silver halide emulsions, by a processing compositionand dye developerpermeable opaque layer. The image-recording silverhalide emulsions have associated therewith respectively a dyeimage-providing material which is a dye developer. The processingcomposition is uniformly applied to the image-recording layers on theside opposite the opaque layer, which can be accomplished by insertingan alkaline composition between the imagerecording layers and a coversheet. The processing composition permeates the image-recording layers,rendering the dye developer nondiffusible in the developed areas, andinitiates diffusion in the nondeveloped areas wherein the dye developercan diffuse through the opaque layer to the image-receiving layer andupon treatment with an onium compound will provide the desired imagedye. Since the element cannot be exposed through the opaque layer, itmust, of course, be exposed from the opposite side. In this system,the-present shifted indophenol developers permit exposure through therequired side and still obtain effective contact with the silver halideemulsion to render the dye developer nondiffusing in the developedareas, thus avoiding severe color contamination; since the shiftedindophenol dye developers can be incorporated in the emulsion layer orpositioned between the emulsion layer and the exposure source withoutsubstantial competitive light absorption, a high-speed photographicsystem with this format based on negative emulsions and diffusible dyeimage-providing substances can now be made. In highly preferredembodiments, image transfer elements of this type are made with asupport having an image-receiving layer thereon and in sequence anopaque layer and at least one imagerecording layer with a cover sheetsuperposed on the image-recording layer to permit uniform application ofa processing liquid to the side of the image-recording layer oppositethe opaque layer. After processing, the cover sheet can remain laminatedwith the support having said layers coated thereon. I

The color film assembly of the present invention may contain varioussilver halide emulsion layers disposed in the usual order, i.e., theblue-sensitive silver halide emulsion layer first with respect to theexposure side, followed by the green-sensitive and red-sensitive silverhalide emulsion layers. If desired, a yellow dye layer of a Carey Leasilver layer may be present between the blue-sensitive andgreen-sensitive silver halide emulsion layer for absorbing or filteringblue radiation that may be transmitted through the blue-sensitive layer.If desired, the selectively sensitized silver'halide emulsion layers maybe disposed in a different order, e.g., the red-sensitive layer firstwith respect to the exposure side, followed by the green-sensitive andblue-sensitive layers, since many of the dye developers of thisinvention which are in association with the sensitive layers do notabsorb substantial radiation in the visible region of the radiationspectrum.

Our novel indophenol dye developers may be employed for all colors or incombination with suitable ad- 3,415,645, 46, and the like. The shifteddye developers having theformul D-(SID) as defined above, are useful inphotographic systems and especially in image transfer systems. Theshifted dye developers of this type are generally diffusible in analkaline medium. In image transfer systems, the shifted dye developer isassociated with a silver halide emulsion wherein the silver halideemulsion is exposed and then treated with an alkaline processingsolution which permeates the layers containing the silver halideemulsion and the shifted dye developer to develop the exposed silverhalide. In the areas where the silver halide emulsion is developed, theshifted dye developer is rendered relatively nondiffusing compared withthe remainder of the shifted dye developer which can diffuse imagewiseto an image-receiving layer wherein it can be mordanted. Upon contactwith an onium salt, which is preferably carried out near or in theimage-receiving layer, the onium indophenoxide image dye is formed.

The developing group D in the above dye developers is generallyresponsible for changes in diffusibility of the shifted dye developerand, upon oxidation by reaction with exposed silver halide or anauxiliary developer, it is preferably oxidized to a relatively immobileform. ln highly preferred embodiments, the group dedeveloper, and ared-sensitive emulsion has associated therewith a shifted cyanindophenol developer.

' Generally, the shifted indophenol dye developers referred to above canbe incorporated in the photographic elements in sufficient quantities toprovide the desired image dye density after processing as known in theart for dye image-providing materials. The concentrations will vary, ofcourse, depending on the type of compound employed, the film unitstructure and the like.

In accordance with this invention when indophenols' are formed in theprocess, they are preferably contacted with onium compounds to formonium indophenoxides. The onium compounds can either be solublecompounds which can be added by contacting the indophenol with asolution of the onium compound or can be high-molecularweight compoundswhich are relatively insoluble in water and can be placed in at leastone layer of the photographic element, such as in the mordant layerwhere the indophenol produces the onium indophenoxide image dye.

In one embodiment, especially useful dye images have been obtainedthrough the combination of indophenols and quaternary ammoniumcompounds. As is known, quaternary ammonium compounds are organiccompounds containing a nitrogen atom having a net positive charge.Generally, they can be considered as derivatives of ammonium compoundswherein the four wherein each R is an organic radical; Y is an anion,e.g., hydroxy, bromide, chloride, toluenesulfonate, etc.; and Zrepresents the atoms necessary to complete a heterocyclic ring. Asexamples of compounds within Formulae l, 2 and 3, mention may be made oftetraethylammonium bromide, N-ethylpyridinium bromide,N,N-diethylpiperidinium bromide, ethylene-bispyridinium bromide,l-ethylpyridinium bromide, l-phenethyl-3-picolinium bromide,tetraalkylammonium salts, cetyltrimethylammonium bromide, polyalkyleneoxide bis-quaternary ammonium salts such as polyethylene oxidebis-pyridinium perchlorate, the heterocyclic quaternary ammonium saltsmentioned which form the methylene bases including 3-methyl-2-ethylisoquinolinium bromide, 3-methylisoquinoliniummethyl-p-toluenesulfonate, phenethylbenzimidazolilum bromide,5,6-'dichloro-lethyl-2-methyl-3-(3-sulfobutyl)benzimidazolium betaincand the pyridinium salts below.

Other useful onium compounds include tertiary sulfonium and quaternaryphosphonium compounds which are represented by the formulae:

(warms and (R)4P X'TM(5) l-ethyl-2-methyl-3- 5 wherein each R is anorganic radical, e.g., alkyl, aralkyl, aryl, etc., groups; and X is ananion, e.g., hydroxy, bromide, chloride, toleuenesulfonate, etc. Asexamples of tertiary sulfonium and quaternary phosphonium compounds,mention may be made of lauryldimethylsulfonium p-toluenesulfonate,nonyldimethylsulfonium p-toluenesulfonate and octyldimethylsulfoniump-toluenesulfonate, butyldimethylsulfonium bromide, triethylsulfoniumbromide, tetraethylphosphonium bromide, dimethylsulfoniump-toluenesulfonate, dodecyldimethylsulfonium p-toluenesulfonate,decyldimethyisulfonium p-toluenesulfonate andethylene-bis-oxymethyltriethylphosphonium bromide.

The 0nium compounds may be used as the hydroxide or as the salt. Whenthe onium compounds are used as the salt, the anion may be a derivativeof any acid. However, it should be noted that when the anion is iodide,such iodide may have deleterious effects on the emulsion and suitableprecautions should be taken if it is to be in contact with the emulsionbefore development is complete. Especially good results are obtainedwhen the onium compounds employed are bromides. V

Useful heterocyclic quaternary ammonium compounds which form themethylene bases diffusible in alkaline solution have the generalformulas: l-'y-phenylpropyl-2-picolinium bromide 2,4-dimethyll-phenethylpyridinium bromide 2,6-dimethyll -phenethylpyridinium bromide5-ethyl-2-methyll-phenethylpyridinium bromide 2-ethyll-phenethylpyridinium bromide l-[3-(N-pyridiniumbromide)propyl1-2-picolinium p-toluenesulfonate pts 5oz-picoline-B-naphthoylmethyl bromidel-B-phenylcarbamoyloxyethyl-2-picolinium bromide 1-methyl-2-picoliniump-toluenesulfonate 1-phenethyl-2,4,6-trimethylpyridinium bromide1-phenethyl-4-n-propylpyridinium bromide4-y-hydroxypropyl-l-phenethylpyridinium bromide and i1-n-heptyl-2-picolinium bromide In highly preferred embodiments of theinvention, the image dye is mordanted in a polymeric material such as apolymer with onium groups thereon. Typical useful mordants of this typeare vinylpyridinium compounds of the type disclosed in U.S. Pat. No.2,484,430 issued Nov. 10, 1949; polymers containing quaternary ammoniumgroups such as disclosed in U.S. Ser. Nos. 734,873 by Cohen et al filedJune 6, 1968, now U.S. Pat. No. 3,625,694, 100,487 by Cohen et a1 filedDec. 21, 1970, now U.S. Pat. No. 3,758,445, 100,491 by Cohen et a1 filedDec. 21, 1979, now U.S. Pat. No. 3,709,690, 709,793 by Cohen et a1 filedMar. 1, 1968, now U.S. Pat. No. 3,639,357, and U.S. Pat. Nos. 3,488,706by Cohen et al issued Jan. 6, 1970, and 3,557,006 by Cohen et a1 issuedJan. 19, 1970; and the like.

In another preferred embodiment, the mordant is an onium coacervatemordant such as disclosed in Bush, U.S. Pat. No 3,271,147 issued Sept.6, 1966.

In FIGS. 4-6, a preferred film unit of the invention is described withthe various elements magnified for purposes of illustration only whereinlike numbers appearing in the various figures refer to like components.

In FIG. 4, rupturable container 1 1 is positioned transverse a leadingedge of the photosensitive laminate and is held in place by bindingmeans 30, which can be a pressure-sensitive tape or the like-whichencloses that edge of the laminate. The other edges of thephotosensitive laminate are sealed together, either directly or with aspacer member, to prevent leakage of processing solution during andafter photographic processing when rupturable container 1 l is brokenopen by pressure-applying members 36 to discharge its contents into thephotosensitive laminate.

In FIG. 5, film unit 10 comprises rupturable container l 1 containing,prior to passing between pressureapplying members 36, an alkalineprocessing composition 12 containing an opacifying agent and aphotosensitive laminate comprising top transparent sheet 25 coated withpolymeric acid layer 24 and polymeric timing layer 23 and aphotosensitive element comprising a transparent support layer 15 coatedwith an image receiving layer 16 associated with an 'onium compound, anopaque reflecting layer 17, a red-sensitive silver halide emulsion layer18 associated with a cyan dye imageproviding material, barrierinterlayer 19, a greensensitive silver halide emulsion layer 20associated with a magenta dye image-providing material, barrierinterlayer 21, and a blue-sensitive silver halide emulsion layer 22associated with a yellow dye image-providing material. Exposure of thefilm unit takes place through the top transparent sheet 25 which ispreferably an actinic radiation transmissive flexible sheet material.

In FIG. 6, film unit 10 has been passed between pressure-applyingmembers 36 such as would be found in a camera, thus causing rupturablecontainer 1 l to collapse and discharge the alkaline processingcomposition 12 containing an opacifying agent between the polymerictiming layer 23 and the blue sensitive silver halide emulsion layer 22.After development and image transfer has taken place, a positive,right-reading image may be viewed through transparent support 15.

The structural integrity of the photosensitive laminate can bemaintained, at least in part, by the adhesive characteristics betweenthe 'various layers of the laminate. However, the adhesion exhibited atthe interface between the polymeric timing layer 23 of top transparentsheet 25 and underlying layer 22 is less than the adhesion at theremaining interfaces of the laminate in order to facilitate distributionof processing composition 12 between these two layers.

The film unit of our invention may be constructed by assembling thevarious parts in an atmosphere maintained at a pressure lower thanatmospheric pressure and by sealing the transparent sheet to thephotosensitive element along their edges in order to prevent theadmission of air between them. The exclusion of air between thetransparent sheet and the photosensitive element is desirable in orderto prevent air bubbles from being entrained in the processingcomposition which would form discontinuities in the positive image.Details of this method of assembly and other methods for assuring auniform distribution of processing composition between two sheets aredescribed in Belgian Pat. No. 711,897.

The film unit of our invention can-also contain a liquid trap at theopposite end from which processing composition is introduced in order totrap any excess processing composition and keep it from being expelledfrom the film unit. The liquid trap may also function to let air escape,if any is present. Such liquid traps are disclosed, for example, inBelgian Pat. No. 71 1,899.

The film unit of our invention may also be processed in the mannerdescribed in Belgian Pat No. 711,898- wherein two sets of pressurerollers are used in order to expel any air between the transparent sheetand the photosensitive element and also to facilitate an evendistribution of processing composition between said sheet and element.The transparent sheet in our film unit may also be fluted along thelength of the side edges, similar to the technique described in BelgianPat. No. 711,898, in order to assist in distributing the processingcomposition evenly between the transparent sheet and the photosensitiveelement.

If it is desired to have residual water in thefilm unit leave the systemafter processing, this may be accomplished by incorporating into thefilm unit a desiccating layer to absorb water or by providing access tothe atmosphere in order to let the water evaporate, e.g., by employing awater-permeable transparent sheet or a water-permeable film support forthe photosensitive element or by allowing water to evaporate through theliquid traps in the film unit as described above, etc.

Rupturable container 1 1 can be of the type disclosed in U.S. Pat. Nos.2,543,181, 2,634,886, 2,653,732, 2,723,051, 3,056,492,. 3,056,491 and3,152,515. In general, such containers comprise a rectangular sheet offluidand air-impervious material folded longitudinally upon itself toform two walls which are sealed to one another along their longitudinaland end margins to form a cavity in which processing composition 12containing an opacifying agent is contained (see FIG. 5). Thelongitudinal marginal seal 35 is made weaker than the end margin sealsso as to become unsealed in response to the hydraulic pressure generatedwithin the fluid contents 12 of the container by the application of acompressive force to the outside walls of the container.

As illustrated in FIGS. 4 and 5, container 1 1 is fixedly positioned andextends transverse a leading edge of the photosensitive laminate so thata compressive force applied to said container will effect aunidirectional discharge of the containers contents between thepolymeric timing layer 23 of top transparent sheet 25 and underlyinglayer 22. in FIG. 5, the weak longitudinal marginal seal 35 is directedtoward the interface between layers 22 and 23 to facilitate thisoperation.

In the performance of a multicolor diffusion transfer process employingfilm unit 10, the unit is exposed to radiation incident on thephotosensitive laminates upper surface through transparent sheet 25, asillustratedin FIG. 5. Subsequent to exposure, the film unit 10 isprocessed by passing it between pressure-applying members 36 in order toapply compressive pressure to frangible container l l and to effectrupture of longitudinal seal 35 and distribution of alkaline processingcomposition 12 containing an opacifying agent between layers 23 and24.0f film unit 10. The alkaline processing composition permeates thesilver halide emulsion layers 22, and 18 to'initiate imagewisedevelopment of the silver halide. Diffusible yellow, ma genta and cyandye image-providing materials are formed from material associated withthe silver halide emulsions in layers 22, 20 and 18 as a function of theimagewise exposure of their-associated emulsions. At least part of theimagewise distributions of mobile yellow-, magentaand cyan-formingmaterials transfer, by diffusion, to the image-receiving layer 16 toprovide a positive dye image therein, preferably upon contact with anonium compound. This positive, right-reading image can then be viewedthrough transparent support layer 15 on' the opaque reflecting layer 17background. Since the receiving layer does not have to be stripped awayfrom the negative portion of the film unit, the composite structure canbe maintained intact subsequent to said processing.

In accordance with the invention, shifted dye developers permit exposurethrough the required side and still retain effective contact with thesilver halide emulsion to render the-dye image-providing materialnondiffusing in the developed areas, thus avoiding severe colorcontamination. The shifted dye developers can generally be incorporatedin the emulsion layer or positioned between the emulsion layer and theexposure source without substantial competitive light absorption, sothat a high-speed photographic system with this format based on negativeemulsions and diffusible dye image-providing substances can now be made.

ln a color film unit according to the invention, each silver halideemulsion layer containing a dye imageproviding material or having thedye image-providing material present in a contiguous layer may beseparated from the other silver halide emulsion layers in the negativeportion of the film unit by materials in addition to those describedabove, including gelatin, calcium alginate, or any of those disclosed inU.S. Pat. No. 3,384,483, polymeric materials such as polyvinylamides asdisclosed in U.S. Pat. No. 3,421,892, or any of those disclosed inFrench Pat. No. 2,028,236 or U.S. Pat. Nos. 2,992,104, 3,043,692,3,044,873, 3,061,428, 3,069,263, 3,069,264, 3,121,011 and 3,427,158.

Generally, except where noted otherwise, the silver halide emulsionlayers in the invention comprise photosensitive silver halide dispersedin gelatin and are about 0.6 to 6 microns in thickness; the dyeimage-providing materials are dispersed in an aqueous alkalinesolutionpermeable polymeric binder, such as gelatin, as a separate layerabout 1 to 7 microns in thickness; and the alkaline solution-permeablepolymeric interlayers, e.g., gelatin, are about 1 to 5 microns inthickness. Of course, these thicknesses are approximate only and can bemodified according to the product desired. ln addition to gelatin, othersuitable hydrophilic materials include both naturally occurringsubstances such as proteins, cellulose derivatives, polysaccharides suchas dextran, gum arabic'and the like; and synthetic polymeric substancessuch as water-soluble polyvinyl compounds like poly(vinylpyrrolidone)acrylamide poly-- mers and the like.

The photographic emulsion layers and other layers of a photographicelement employed in the practice of this invention can also contain,alone or in combination with hydrophilic, water-permeable colloids,other synthetic polymeric compounds such as dispersed vinyl compoundssuch as in latex form, and particularly those which increase thedimensional stability of the photographic materials. Suitable syntheticpolymers include those described, for example, in U.S. Pat. Nos.3,142,568 by Nottorf issued July 28, 1964, 3,193,386 by White issuedJuly 6, 1965, 3,062,674 by Houck et al issued Nov. 6, I962, 3,220,844 byHouck et al issued Nov. 30, 1965, 3,287,289 by Ream et al issued Nov.22, 1966, and 3,411,91l by Dykstra issued Nov. 19, 1968. Particularlyeffective are waterinsoluble polymers of alkyl acrylates andmethacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates,those which have cross-linking sites which facilitate hardening orcuring, and those having recurring sulfobetaine units as described inDykstra, Canadian Pat, No. 774,054.

Any material can be employed as the image-receiving layer in thisinvention as long as the desired function of mordanting or otherwisefixing the dye images will be obtained. The particular material chosenwill, of

course, depend upon the dye image to be mordanted as mentionedhereinbefore. In one embodiment, the photographic elements of thisinvention contain an imagereceiving layer which comprises apolyvinylpyridine mordant. However, the dyes formed with thepolyvinylpyridine mordant appear to be distinguished from those formedwith an onium mordant in that they can be removed from the mordant layerby repeated washings.

Use of a pl-l-lowering layer in the film unit of the invention willusually increase the stability of the transferred image. Generally, thepH-lowering layer will effect a reduction in the pH of the image layerfrom about 13 and 14 to at least 1 1 and preferably 5-8 within a shorttime after imbibition. For example, polymeric acids as disclosed in US.Pat. No. 3,362,819 may be employed. Such polymeric acids reduce the pHof the film unit after development to terminate development andsubstantially reduce further dye transfer and thus stabilize the dyeimage. Such polymeric acids comprise polymers containing acid groups,such as carboxylic acid and sulfonic acid groups, which are capable offorming salts with alkali metals,.such as sodium or potassium, or withorganic bases, particularly quaternary ammonium bases, such astetramethyl ammonium hydroxide. The polymers can also containpotentially acid-yielding groups such as anhydrides or lactones or othergroups which are capable of reacting with bases to capture and retainthem. Generally, the most useful polymeric acids contain free carboxylgroups, being insoluble in water in the free acid form and which formwatersoluble sodium and/or potassium salts. Examples of such polymericacids include dibasic acid half-ester derivatives of cellulose, whichderivatives contain free carboxyl groups, e.g., cellulose acetatehydrogen phthalate, cellulose acetate hydrogen glutarate, celluloseacetate hydrogen succinate, ethyl cellulose hydrogen succinate, ethylcellulose acetate hydrogen succinate, cellulose acetate succinatehydrogen phthalate; ether and ester derivatives of cellulose modifiedwith sulfoanhydrides, e.g., with ortho-sulfobenzoic anhydride;polystyrene sulfonic acid; carboxymethyl cellulose; polyvinyl hydrogenphthalate; polyvinyl acetate hydrogen phthalate; polyacrylic acid,acetals of polyvinyl alcohol with carboxy or sulfo-substitutedaldehydes, e.g., mor p-benzaldehyde sulfonic acid or carboxylic acid;partial esters -of ethylene/maleic anhydride copolymers; partial estersof methylvinyl ether/ maleic anhydride copolymers; etc. In addition,solid monomeric acid materials could also be used such as palmitic acid,oxalic acid, sebacic acid, hydrocinnamic acid, metanilic acid,paratoluenesulfonic acid and benzenedisulfonic acid. Othersuitable'materials are disclosed in US. Pat. Nos. 3,422,075 and2,635,048.

The pH-loweri'ng layer is usually about 0.3 to about mils in thicknessand can be located in the receiver portion of the film unit between thesupport and the image-receiving layer, on the cover sheet, or it can belocated anywhere within the film unit as long as the desired function isobtained.

An inert timing or spacer layer coated over the pH- lowering layer mayalso be used to time" or control the pH reduction of the film unit as afunction of the rate at which the alkali diffuses through the inertspacer layer. This timing layer can also be used effectively to isolateoxidizing materials in a layer adjacent the image-receiving layerwherein oxidant will be released after alkali breakdown of the timinglayer. Examples of such timing layers include gelatin, polyvinyl alcoholor any of those disclosed in US. Pat. No. 3,455,686. The timing layer isalso effective in evening out the various reaction rates over a widerange of temperatures, e.g., premature pH reduction is prevented whenimbibition is effected at temperatures above room temperature, forexample, at 95 to 100 F. The timing layer is usually about O.l to about0.7 mil in thickness. Especially good results are obtained when thetiming layer comprises a hydrolyzable polymer or a mixture of suchpolymers which are slowly hydrolyzed by the processing composition.Examples of such hydrolyzable poly mers include polyvinly acetate,polyamides, cellulose esters, etc.

The alkaline processing composition employed in this invention is theconventional aqueous solution of an alkaline material, e.g., sodiumhydroxide, sodium carbonate or an amine such as diethylamine, preferablypossessing a pH in excess of 12, and preferably containing an auxiliarydeveloping'agent. The solution also preferably contains aviscosity-increasing compound such as a high-molecular-weight polymer,e.g., a watersoluble ether inert to alkaline solutions such'ashydroxyethyl cellulose or alkali metal salts of carboxymethyl cellulosesuch as sodium carboxymethyl cellulose. A

concentration of viscosity-increasing compound of about 1 to about 5% byweight of the processing solution is preferred which will impart theretoa viscosity of about cps. to about 200,000 cps. If desired, an adhesivemay be added to the processing composition to increase further theadhesion of the transparent sheet to the photosensitive element afterprocessing.

The alkaline processing composition employed in this invention can alsocontain an auxiliary or accelerating developing agent which does notcontain the structure D-(SlD) as defined above. Typical useful auxiliarydeveloping agents (reducing agents) are pmethylaminophenol,2,4-diaminophenol, pbenzylaminophenol, hydrozuinone, toluhydroquinone,phenylhydroquinone, 4-methylphenylhydroquinone, etc. A plurality ofauxiliary or accelerating developing agents such as those. disclosed inUS. Pat. No. 3,039,869 can also be employed. Such auxiliary oraccelerating developing agents can be' employed in the liquid processingcomposition or may be contained, at least in part, in any layer orlayers of the film unit such as the silver halide emulsion layers, thedye imageproviding material layers, interlayers, image-receiving layer,etc., and are preferably coated in the layers of the photosensitiveelement.

The alkaline processing composition employed in this invention can alsocontain a desensitizing agent such as methylene blue, nitro-substitutedheterocyclic compounds, 4,4'-bipyridinium salts, etc., to insure thatthe photosensitive element is not further exposed after it is removedfrom the camera for processing.

While the alkaline processing composition used in this invention can beemployed in a rupturable container, as described previously, tofacilitate conveniently the introduction of processing composition intothe film unit between the transparent sheet and the photosensitiveelement, other means of discharging processing composition within thefilm unit could also be employed, e.g., interjecting processing solutionwith communicating members similar to hypodermic syringes which areattached either to a camera or camera cartridge, as described in Harvey,US. Pat. No. 3,352,674 issued November 14, 1967.

Any opacifying agent can be employed in the processing composition incertain embodiments of our invention. Examples of opacifying agentsinclude carbon black, barium sulfate, zinc oxide, barium stearate,silver flake, silicates, alumina, zirconium oxide, zirconium acetylacetate, sodium zirconium sulfate, kaolin, mica, titanium dioxide,organic dyes such as the nigrosines, or mixtures thereof in widelyvarying amounts depending upon the degree of opacity desired. Ingeneral, the concentration of opacifying agent should be sufficient toprevent further exposure of the film units silver halide emulsion oremulsions by ambient actinic radiation transversing through the toptransparent sheet subsequent to distribution of the processing solutionbetween the top transparent sheet and the underlying layer adjacentthereto. For example, carbon black or titanium dioxide will generallyprovide sufficient opacity when they are present in the processingsolution in an amount of from about 5 to 40% by weight. After theprocessing solution and opacifying agent have been distributed into thefilm unit, processing may take place out of the camera in the presenceof actinic radiation in view of the fact that the silver halide emulsionor emulsions of the laminate are appropriately protected by incidentradiation, at one major surface by the opaque processing composition andat the remaining major surface by the alkaline solution-permeable opaquelayer. Opaque binding tapes can also be used to prevent edge leakage ofactinic radiation incident on the silver halide emulsion.

; When titanium dioxide or other white pigments are employed as theopacifying agent in the processing composition in our invention, it mayalso be desirable to employ in cooperative relationship therewith a pH-sensitive opacifying dye such as a phthalein dye. Such dyes arelight-absorbing or colored at the pH at which image formation iseffected and colorless or not lightabsorbi'ng at a lower pH. Otherdetails concerning these opacifying dyes are described in French Pat.No. 2,026,927.

The alkaline solutiompermeable, sus bstantially opaque, light-reflectivelayer' in the photographic film unit of our invention can generallycomprise any opacifier dispersed in a binder as long as it has thedesired properties. Particularly desirable are white lightrefelectivelayers since they would be esthetically pleasing backgrounds on which toview a transferred desired for reflection'of incident radiation.Suitable opacifying agents include titanium dioxide, bariumsulfate;-zinc oxide, barium stearate, silver flake, silicates, alumina,zirconium oxide, airconium acetyl acetate, sodium zirconium sulfate,kaolin, mica, or mixtures thereof in widely varying amounts dependingupon the degree of opacity desired. The opacifying agents may bedispersed in any binder such as an alkaline solutionpermeable polymericmatrix such as, for example, gelatin, polyvinyl alcohoLand the like.Brightening agents such as the stilbenes, coumarins, triazines andoxazoles can also be added to the light-reflective layer, if desired.When it is desired to increase the opacifying capacity of thelight-reflective layer, dark-colored opacifying agents may be added toit, e.g., carbon black, nigrosine dyes, etc. Another technique toincrease the opacifying capaicty of the light-reflective layer is toemploy a separate opaque layer underneath it comprising, e.g., carbonblack, nigrosine dyes, etc., dispersed in an alkaline solution-permeablepolymeric matrix such as, for example,- gelatin, polyvinyl alcohol, andthe like. Such an opaque layer would generally have a density of atleast 4 and preferably greater than 7 and would be substantially opaqueto actinic radiation. The opaque layer may also be combined with adeveloper scavenger layer if one is present. The light-reflective andopaque layers are generally 1 to 6 mils in thickness, although they canbe varied depending upon the opacifying agent employed, the degree ofopacity desired,

etc.

When transparent sheets are used in film assemblies of this invention,they can be any transparent material as long as it does notdeleteriously affect the photographic properties of the film unit and isdimensionally stable. Typical actinic radiation-transmissive flexiblesheet materials include cellulose nitrate film, cellulose acetate film,poly(vinyl acetal) film, polystyrene film, poly(ethyleneterephthalate)film, poly-carbonate film, poly-a-olefins such as polyethylene andpolypropylene film, and related films or resinous materials, as well asglass. The transparent sheet is usually about 2 to 6 mils in thicknessand may contain an ultraviolet absorber for exposure control if desired.in addition, an adhesive tion may be present on the transparent sheet inorder I to increase its adhesion to the photosensitive element afterprocessing.

Whentransparent supports are used in film assemblies of this invention,they can be any of the materials mentioned above for the transparentsheet. If desired, an ultraviolet-absorbing material can be employed inthe support to prevent the dye images from fading due to ultravioletlight.

The photosensitive substances used in this invention are preferablysilver halide compositions and can comprise silver chloride, silverbromide, silver bromoiodide, silver chlorobromoiodide and the like, ormixtures thereof. The emulsions may be coarseor finegrain and can beprepared by any of the well-known procedures, e.g., single-jetemulsions, double-jet emulsions, such asLippmann emulsions, ammoniacalemulsions, thiocyanate or thioether ripened emulsions such as thosedescribed in U.S. Pat. No. 2,222,264 by Nietz et al, 3,320,069 byIllingsworth, and 3,271,157 by Mc- Bride. Surfaceimage emulsions can beused or internal-image emulsions can be used such as those described inU.S. Pat. Nos. 2,592,250 by Davey et al,

3,204,313 by Porter et al, and 3,447,927 by Bacon et al. The emulsionsmay be regular-grain emulsions such as the type described in Klein andMoisar, J. Phot, Sci., Vol. 12, No. 5, Sept./Oct., 1964, pp. 242251..lfdesired, mixtures or surface-and internal-image emulsions can be used asdescribed in Luckey et al, U.S. Pat. No. 2,996,382.

' Negative-type emulsions are generally preferred, but direct-positiveemulsions can be used if desired. Typical direct-positive emulsionsinclude those described in U.S. Pat. Nos. 2,184,013 by Leermakers,2,541,472 by Kendall et al, 3,367,778 by Berriman, 3,501,307 by 111-ingsworth et a1 issued March 17, 1970, 2,563,785 by Ives, 2,456,953 byKnott et a1 and 2,861,885 by Land, British Pat. No. 723,019 bySchouwenaars, and U.S. Ser. Nos. 123,005 by Evans filed Mar. 10, 1971,now U.S. Pat. No. 3,761,276, 123,006 by Milton filed Mar. 10, 1971, nowU.S. Pat. No. 3,761,266, 123,007 by Gilman et al filed'Mar. 10, 1971,now U.S. Pat. No. 3,761,267, 154,154 by Collier et al filed June 17,1971 now U.S. PAt. No. 3,726,140, 154,155 by Gilman et a1 filed June 17,1971, now abandoned and 154,224 by Gilman et a1 filed June 17, 1971, nowU.S. Pat. No. 3,730,723.

Generally, in the photographic elements referred to above, a positiveimage record is obtain-in an imagereceiving layer by mordanting thediffusible imageproviding material which is not immobilized or remainsdiffusible in the photosensitive portion of the film unit. it is alsoappreciated that the photosensitive element contains an image recordwhich provides a useful image product. In one instance, the mobile ordiffusible materials can be washed out after exposure to produce anegative image record. in another embodiment, the silver halide emulsioncan be selected to produce a positive image record in the photosensitiveportion of the film element.

The invention can be further illustrated by the following exampleswherein the compounds identified by roman numerals are furtheridentified structurally in the foregoing specification.

1 EXAMPLE 1 A. Preparation of Intermediate I-A rhoomoomw A suspension of12.4 g. (0.04 M.) of compound I in 50 ml. dry benzene is refluxed with10 ml. thionyl chloride for 30 minutes. The benzene is removed, yieldingan oil which is treated with 10.8 g. (0.04 M.) of compound 2 and ml. ofN,N-dimethylaniline in acetone solution. This mixture is allowed tostand overnight, the solvent is removed and the residue isrecrystallized from acetonitrile to yield 12.4 g. of solid (IntermediateI-A), m.p. l63-l67 C. Thin-layer chromatography shows one component. TheIR spectrum agrees with the assigned structure.

B. Preparation of Intermediate 'I-B A suspension of 8.4 g. (0.015 M.)oflntermediate I-A in 300 ml. of dimethoxyethane is treated with 0.58 g.(0.015 M.) of NaI-I dispersion. After stirring for 30 minutes, 5.9 g.(0.015 M.) of compound 4 is added and the mixture is allowed to standovernight. The solvent is removed, yielding an oil which is dissolved inchloroform and filtered through a silica gel pad. After re moval of thesolvent, the residue is recrystallized from benzene-cyclohexane to give3 g. of Intermediate I-B. Thin-layer chromatography shows one component.The IR spectrum agrees with the assigned structure. Compound 4 is:

C. Preparation of Compound I (shifted yellow indophenol dye developer) gA solution of g. (0.0l2 M.) of Intermediate I-B in 200 ml. of methanolis refluxed for 1 hour in a nitrogen atmosphere with 2.8 g. (0.05 M.) ofpotassium hydrox ide dissolved in water. After cooling, the reactionmixture is acidified with acetic acid and extracted with ether. Theether extract is concentrated to an oil, then recrystallized frombenzene-ethyl acetate-cyclohexane to give 1 g. of Compound I. Thin-layerchromatography shows one component. The NMR and IR spectra agree withthe assigned structure.

EXAMPLE 2 This example demonstrates in a nonimage-forming format theproperty of a shifted dye developoer of undergoing a spectral-absorptionchange upon contact with a mordant such as an organic onium compound.

A. A supported single-layer gelatinous coating, containing 250 mg. ofgelatin and mg. of Compound I per square foot of coating, is dried andspectrophotometrically evaluated. The spectrophotometric absorptionprofile of Compound I contained in the soprepared coating is representedby Curve A in FIG. 2.

B. A sample of the above-described coating is immersed for 1 minute in amordant solution whose composition is given below:

hexadecyltrimethylanunonium bromide 5 g. K i-IP0 (0.5 M.) 430 ml. KH PQ(1.5 M.) 70 ml. water to 1 liter Upon removal from the solution, thesample is dried and spectrophotometrically evaluated. The absorptionprofile of Compound I in the so-treated sample is represented by Curve Bin FIG. 2.

A comparison of Curves A and B in FIG. 2 shows the compounds initial lowabsorption and its desirable final high absorption of blue light.

EXAMPLE-3 potassium hydroxide hydroxyethyl cellulose water to l literUpon separation of the gelatin coating from the receiver, the lattercontains a uniformly distributed dense yellow dye. The receiver iswashed for 3 minutes without appreciable change in the appearance of theyellow dye.

EXAMPLE 4 A supported multilayer photographic element is coated asfollows:

I. support;

2. layer containing 250.mg./ft. of gelatin, 70 mg./ft.

of Compound I and 70 mg./ft. of diethyl lauramide;

3. layer containing 250 mg./ft. of gelatin and a silver halide emulsionat 200 mg./ft. of silver;.

4. layer containing mg./ft.2 of gelatin.

A sample of the above-described coating is exposed through agraduated-density test object and processed in the presence of a viscousdeveloping solution whose composition is shown below, while in contactfor 30 seconds with a receiver containing the mordant of Example 3. Uponseparation of the coating sample from the receiver, the latter containsa well-defined positive yellow umage of the photographed test object.

Developing Solution sodium hydroxide g.l-phenyl-4-methyl-4-hydroxymethyl-3- 0.75 g. Eyrazo'lidone ydroxyethylcellulose g. water to 1 liter EXAMPLE 5 ceiver, the latter contains adense yellow dye in the area which, during the transfer cycle, has beenopposite the unexposed section of the emulsion coating. The rceiver iswashedfor 3 minutes without appreciable change in the appearance of theyellow dye.

B. When the procedure described in section (A) above is repeated with aprocessing liquid which consists of only 40 g, potassium hydroxide andg. hydroxyethyl cellulose per liter of solution, (i.e., the auxiliarydeveloping agent has been omitted), the receiver contains yellow dye inboth areas of contact. In this embodiment, the auxiliary developingagent is desirable to provide immobilizing reactions to obtain goodimage discrimination.

EXAMPLE 6 ocoocnn CH2COOH I I 0 c 0 0 can "NHCOCaFl A solution (6-1) indry tetrahydrofuran is treated with a mixture of thionyl chloride andN,N-dimethylformamide in dry benzene and heated for 30 minutes. Thesolvent is removed under reduced pressure to give the acid chloride,m.p. 5053 C. The acid chloride is dissolved in dry dioxane and added toa mixture of (62) and quinoline in dry dioxane. After standing at roomtemperature, the solid is collected and recrystallized from acetonitrileto give Intermediate 6-A, m.p. l98-200 C.

A solution of Intermediate 6-A in tetrahydrofuran is treated with (6-3),followed by a solution of sodium bicarbonate in water and methyl alcoholand stirred for 1 hour. Water is added, the solid is collected,dissolved in chloroform and chromatographed on silica gel to giveCompound 6, mp. l36l 37 C. Compound (6-3) is as follows:

Compound 6 is as follows:

Compound 6 is incorporated in a gelatin layer coated on a support and isfound to transfer a cyan dye to a quaternary mordant when contacted withan alkaline processing solution with a pH of 14. The dye remains cyanwhen the pH is then adjusted to about 7.

. EXAMPLE 7 Preparation of a Magenta Shifted Dye Developer (1)COOC2H: 1.SO C12 35 a l I ('300 o C2115 NH- =0 C1 A suspension of (7-b l) in drybenzene is refluxed with thionyl chloride and N,N-dimethylformamide for20 minutes. The solvent is removed under reduced pressure and theresidue is dissolved in acetic acid and added to a solution of (7-2) andsodium acetate in acetic acid. The mixture is stirred for 2 hours,allowed to stand overnight, then poured into water. After neutralizingwith sodium bicarbonate, the solid is collected and recrystallized fromethyl acetate to give ln termediate 7-A, mp. 135-136 C.

A solution of Intermediate 7-A in ethyl acetate and tetrahydrofuran istreated with sodium bicarbonate, followed by Compound 7-3), then stirredfor 1 hour. Water is added, the mixture is filtered through celite andthe filtrate is extracted with chloroform. After washing with water, theorganic layer is separated, dried and concentrated under reducedpressure. The residue is chromatographed on silica gel to yieldintermediate 7-B.

Compound (7-D) is as follows:

N (:1 s l l llr I A solution of Intermediate 7-8 in tetrahydrofuran andpyridine is treated with a 3% sodium carbonate solution and refluxed for5 hours under a nitrogen atmosphere. After cooling, the solution ispoured into a dilute acetic acid solution and the solid is collected togive Compound II identified above.

In certain embodiments according to this invention, the shifted dyedevelopers of this invention can be prepared as illustrated in thefollowing example by further reacting the oxichromic compounds ofLestina and Bush, U.S. Ser. No. 206,949, entitled Oxichromic Compounds,Stabilized Oxichromic Compounds and Processes for Preparing Same filedDec. 10, 1971, and incorporated herein by reference, now abandoned andrefiled as US. Ser. No. 426,177.

EXAMPLE 8 The oxichromic compound 4-(3,5-dichloro-4-hydroxyanilino)-2-[5-(2,5-dihydroxyphenyl)pentanoylamido]-5-(4-pentoxybenzamido)phenol (1.449,2.11 X 10 moles), prepared according to Lestina and Bush, US. Ser. No.206,949, Example 2, is dissolved in 300 ml. of a mixture of 80% byvolume acetonitrile and 20% by volume N,N-dimethylformamide and thesolution is made 0.1 molar with sodium perchlorate. The solution isoxidized by controlled potential electrolysis in a twocompartment cellusing a potentiostat for control and platinum electrodes at a potentialof +0.55 v. until the current has decayed to 10% of its original value.The progress of the reaction is monitored by occasionally recording acurrent-voltage curve. After 375.1 coulombs (2.05 electrons/moleculehave passed, the first oxidation wave (E of the lecuo dye has diminishedto approximately 5% of its original height, whereas the B. A coatingcontaining a silver halide emulsion is prepared by coating on acellulose acetate support the following layers:

1. layer containing .125 mg./ft. of gelatin, 75 mg./ft. of diethyllauramide and 50 mg./ft. of Compound IV;

2. layer containing a monodispersed silver bromide emulsion at 100 mg.of Ag/ftF, l0 mg./ft. of l-phenyl-3-pyrazolidone and 100 mg/ft. of gela-3. overcoat containing 80 mg./ft. of gelatin.

The nonsilver coating is evaluated on a spectrophotometer and gives Amzuat 590 nm. with a Dmax of second wave (E has retained its originalheight. The

red solution is filtered and water is added dropwise, causingprecipitation of the product. The red solid is collected by filtration,washed several times with water and dried under reduced pressure. Theyield is 1.4 g. or about 100%.- The current yield is also 100%. Afterrecrystallization from ethanol, m.p.= ZOO-201 C.

The compound has the formula:

EXAMPLE 9 0.55 which is shown as line A of FIG. 3.

. A portion of the nonsilver coating is soaked in a 5% 1-phenyl-3-pyrazolidone solution (H 0 and methanol) for 5 minutes wherein thecolor substantially disappears. A spectrophotometric absorption curve ofthis potassium hydroxide hydroxyethyl cellulose water to make 1 literThe receiver sheet is peeled from the coated sample after processingwith substantially no dye image apparent in the treated coating. Afterabout 2-5 seconds exposure to air, the reflective density of the dyetransferred from the treated sample is 2.40 with a 30-second transfer,whereas the density from the untreated sample is 1.80 after a 5-minutetransfer as evidenced by line C of FIG. 3.

The coatings containing the silver halide emulsion are given a steppedexposure and processed for 60 seconds with the processing compositionabove while in contact with the mordanted receiver sheet above.

There is substantially no dye in the receiver immediately after thereceiver sheet is peeled from the photosensitive element. However, after2-5 seconds of contact with air substantial dye density is observed inthe receiver sheet.

The incorporation of the reducing agent l-phenyl-3- pyrazolidone in thephotographic element, along with the shifted indophenol dye developer,appears to provide substantially no absorption of light by the shifteddye developer and also provides faster transfer of dye to theimage-receiving layer.

When the untreated coatings are developed with a processing solutioncontaining 5 g. per liter of ascorbic acid (reducing agent), fasttransfer times are also obtained.

EXAMPLE 10 The oxichromic compound 4-(3,5-dichloro-4-hydroxyanilino)-3-{ 3-[5-(2,5- dihydroxyphenyl)pentanoylamido]phenylcarbamoyl} l-phenyl-2-pyraioline-5-one, preparedaccording to Example l-C of Stern and Machiele, U.S. Ser. No. 206,926filed Dec. 10, 1971, and incorporated herein by reference, is subjectedto hydrogenolysis to remove the masking groups on the developing moietyaccording to Example l-F of Stern and Machiele, U.S. Ser. No. 206,926,and then subjected to-aerial oxidation to produce the shifted dyebelieved to have the formula:

(CIIQ),WCONIIK lkz (101 11. (in lNll l\I( U Compound V EXAMPLE ll:

The shifted indophenol dye developers can be incorporated into themulticolor photosensitive element of a film transfer unit as disclosedin US. Pat. No. 2,983,606, Belgian Pat. Nos. 757,959 and 757,960 grantedApr. 23, i971, or Lestina and Bush, US. Ser. No. 206,836 filed Dec. 10,197i entitled Oxichromic Compounds, now abandoned and refiled as U.S.Ser. No. 308,869, all of which are incorporated herein by reference.Compound V is ineorporated in association with a green-sensitive silverhalide emulsion, Compound IV is incorporated in association with theredsensitive silver halide emulsion and Compound I is incorporated inassociation with the blue-sensitive silver halide emulsion layer.Compounds I, IV and V can be coated in the respective silver halideemulsion layers, on the exposure side of the silver halide emulsionlayers, or under the emulsion layer with respect to exposure; however,the first two locations are preferred. An auxiliary developer andpreferably a reducing agent, such as l-phenyl-3-pyrazolidone, areincorporated in the photographic element in association with therespective shifted dye developers.

The image-receiving layer contains a dye mordant which is preferably an'onium compound. Suitable onium mordants are in coacervate ofN-n-hexadecyl- N-morpholinium ethosulfate and'methyl-tri-ndodecylammonium p-toluenesulfonate, the mordan tN-n-octadecyltributylammonium bromide, and the like.

Good three-color image transfers are obtained upon processing with analkaline processing solution and the image dyes remain stable even whenthe pH is reduced to about 7.

Although the invention has been described in considerable detail withparticular reference to certain preferred embodiments thereof,variations and modifications can be effected within the spirit and scopeof the invention.

We claim:

1. Aphotographic element comprising a support and at least one layerthereon containing a photographic silver halide having associatedtherewith a dye developer which is diffusible in an alkaline processingmedium and has the general formula:

D-(SlD) wherein D- is an aromatic nucleus polysubstituted with hydroxygroups, amino groups or alkylamino groups to provide a group which iscapable of developing silver halide, and (SlD) is an indophenol dyemoiety.

2. A photographic element according to claim 1 wherein (SID) is a grouphaving the formula:

,ene group containing from 6 to 20 carbon atoms.

3. A photographic element according to claim 2 wherein Ar is a phenylenegroup.

,4. A photographic element according to claim 1 which comprises at leastone layer containing an onium. salt in water-permeable association withsaid dy'e developer.

5. A photographic element according to claim 1 wherein D comprises anaromatic nucleus which contains at least two substituents thereon fromthe class of hydroxy groups, primary amino groups or alkylamino groups.

6. A photographic element according to claim 1 wherein D- is ahydroquinone group.

7. A photographic element according to claim 1 wherein said elementcomprises at least two separate layers containing a silver halideemulsion, each having aseparate dye developer of saidformula associatedtherewith.

8. A photographic element according to claim 1 wherein said elementcomprises a blue-sensitive silver .halide emulsion layer havingassociated therewith a yellow-forming indophenol. dye developer, agreensensitive silver halide emulsion layer having associated therewitha magenta-forming indophenol dye developer, and a red-sensitive silverhalide emulsion layer having associated therewith a cyan-formingindophenol dye developer.

9. A photographic element according to claim 8 wherein said cyan-formingdye developer, said magenta-forming dye developer and saidyellow-forming dye developer are each of said formula:

D-(SlD) and said element contains an image-receiving layer.

10. A photographic element according to claim 2 wherein Ar is aphenylene group and said OH group is para to said nitrogen atom.

11. A photographic element according to claim 1 wherein said dyedeveloper has the formula:

wherein D- is an aromatic nucleus polysubstituted with hydroxy groups,primary amino groups or alkylamino groups to provide a group which iscapable of developing silver halide, Ar is a phenylene group, and (PYZ)is a pyrazolone coupler radical or a pyrazolotriazole coupler connectedat its coupling position to said nitrogen atom.

12. A photographic element according to claim 1 wherein said dyedeveloper has the formula:

wherein D- is an aromatic nucleus polysubstituted with hydroxy groups,primary amino groups or alkylarnino groups to provide a group which iscapable of developing silver halide, Ar is a phenylene group, and (KMC)is an open-chain ketomethylene coupler radical connected at its couplingposition to said nitrogen atom.

29 13. A photographic element according to claim 1 wherein said dyedeveloper has the formula:

wherein D- is an aromatic nucleus polysubstituted with hydroxy groups,primary amino groups or alkylamino groups to provide a group which iscapable of developing silver halide, Ar is a phenylene group, and (PhC)is a phenolic coupler radical connected at its coupling position to saidnitrogen atom.

14. A photographic film unit comprising:

a. a photosensitive element comprising a support having thereon a layercontaining a silver halide composition having associated therewith a dyedeveloper which is diffusible in an alkaline processing medium and hasthe formula:

D-(SID) wherein D- is an aromatic nucleus polysubstituted with hydroxygroups, primary amino groups or alkylamino groups to provide agroupwhich is capable of developing silver halide, and (SID) is anindophenol dye moiy;

b. a dye image-receiving layer; and

c. means for discharging an alkaline processing composition-within saidfilm unit. 2

15. The film unit of claim 14 wherein said imagereceiving layer islocated in said photosensitive element between said support and any saidsilver halide .composition layer. 7

16. A film unit according to claim 14 containing an onium salt inliquid-permeable association with said dye developer and which issequestered from said dye developer until contact with said liquidprocessing composition 17. The film unit of claim 14 wherein saidphotosensitive element comprises a support having thereon:

a. a red-sensitive silver halide emulsion layer having associatedtherewith a cyan-forming dye developer;

b a green-sensitive silver halide emulsion layer having associatedtherewith a magenta-forming dye developer; and

c. a blue-sensitive silver halide emulsion layer having associatedtherewith a yellow-forming dye developer.

18. A film unit according to'claim 14 wherein said dye image-receivinglayer is coated on a separate support and is adapted to be superposed onsaid photosensitive element after exposure thereof.

19. A film unit according to claim 14 wherein said image-receiving layeris coated adjacent said silver halide emulsion layers with an opaquelayer between said silver halide emulsion layers and saidimage-receiving layer.

20. A film unit according to claim 14 wherein said discharging meanscomprises a rupturable container and is so positioned during processingof said film unit that a compressive force applied to said container bypressure-applying members will effect a discharge of the containerscontents between said dye imagereceiving layer and the layer most remotefrom the support of said photosensitive element.

21. A film unit according to claim 14 wherein said discharging meanscomprises a rupturable container and is so positioned during processingof said film unit that a compressive force applied to said container byLII pressure-applying members will effect a discharge of the containerscontents between the layer most remote from the support of saidphotosensitive element and a cover sheet superposed on saidphotosensitive element.

Y 22. A photographic film unit according to claim 14 wherein said dyedeveloper has the formula:

(Hill:

23. A photographic film unit according to claim 14 wherein said dyedeveloper has the formula:

24. A photographic film unit according to claim 14 wherein said dyedeveloper has the formula:

25. A process for producing a photographic transfer image comprising:

a. imagewise-exposing a photosensitive element comprising a supporthaving thereon a layer containing a silver halide composition havingassociated therewith a dye developer which is diffusible in an alkalineprocessing medium and has the formula:

D-(SID) wherein D- is an aromatic nucleus polysubstituted with hydroxygroups, amino groups or alkylamino groups to provide a group which iscapable of developing silver halide, and (SID) is an indophenol dyemoiety;

b. treating said photosensitive element with an alkaline processingcomposition to effect development of said exposed silver halidecomposition layer;

c. forming an imagewise distribution of said dye developer as a functionof development of said silver halide composition layer;

d. at least a portion of said imagewise distribution of diffusible dyevdeveloper diffusing to an imagereceiving layer; and

e. contacting said dye developer with an onium compound at some pointafter imagewise exposure.

26. A process according to claim wherein said image-receiving layercontains an onium compound.

27. The process of claim 25 wherein said treatment step b) is effectedby:

a. superposing over the layer outermost from the support of 7 saidphotosensitive element said imagereceiving layer coated on a support;

b. positioning a rupturable container containing said alkalineprocessing composition between said exposed photosensitive element" andsaid imagereceiving layer; and

c. applying a compressive force to said container to effect a dischargeof the containers contents between said outermost layer of said exposedphotosensitive element and said image-receiving layer.

28. The process of claim 25 wherein said support is transparent and saidimage-receiving layer is located between said support and said silverhalide composition layer, and said treatment is effected by applying acompressive force to a rupturable container located between theoutermost layer of said photosensitive element and a transparentsuperposed cover sheet, and wherein said container contains an alkalineprocessing composition which is discharged by said compressive force.

wherein D- is an aromatic nucleus polysubstituted with hydroxy groups,amino groups or alkylamino groups to provide a group which is capable ofdeveloping silver halide, (SID) is an indophenol dye moiety, and M is anonium group.

31. A photographic product according to claim 30 wherein M is aquaternary ammonium group.

32. A photographic product according to claim 30 wherein said oniumindophenoxide has the formula:-

wherein D- is an aromatic nucleus polysubstituted with hydroxy groups,amino groups or alkylamino groups to provide a group which is capable ofdeveloping silver halide, (COUP) is a photographic color coupler, Ar isan arylene group containing from about 6 to about 20 carbon atoms, and Mis an onium group.

33. A photographic product according to claim 32 wherein (COUP) is anopen-chain ketomethylene color coupler group connected at its couplingposition to said nitrogen atom.

34. A photographic product according to claim 32 wherein (COUP) is apyrazolone or pyrazolotriazole color coupler group connected at itscoupling position to said nitrogen atom.

35. A photographic product according to claim 32 wherein (COUP) is aphenolic color coupler connected at its coupling position to saidnitrogen atom.

36. A photographic product according to claim 30 which contains 1) anonium indophenoxide of said formula wherein (SID) comprises a phenoliccolor coupler, 2) an onium indophenoxide of said formula wherein (811))comprises an open-chain ketomethylene color coupler and 3) an 'oniumindophenoxide of said formula wherein (SlD) comprises a pyrazolone orpyrazolotriazole color coupler.

37. A photographic product according to claim 30 wherein saidimage-receiving layer comprises a polymer with onium groups thereon.

38. A photographic product according to claim 30 wherein said Mrepresents an immobile *onium compound which is present in saidimage-receiving layer at concentrations of about 25 mg. to 1000 mg. persquare foot.

- 39. A photographic product according to claim 30 wherein D- is ahydroquinone group or an oxidized hydroquinone group.

323 UNITED STATES PATENT OFFICE CERTIFICATE or CORRECTION Patent No. 2,85 L,9 L5 Dated December 17, 197A Inventor(s) Walter Monroe Bush andDaniel Francis Reardon It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

{Column 1, lines 58-59, image-recordng" should read --imagerecording---.Column 3, line 20, openchain should read open-Chain---. Column 5, lines63-6 L, "greensensitive should read ---greensensitive-. Column 10, line51, "therwith' should read -therewith. Column 11, line 55, that part offormula reading phenethylbenzimidazolilum" should readphenethylbenzimidazolium-3 line 65:

(R) 2+X-TM(L should read (R) s-+X last line:

(5) (R) TP*T "TM(5) should read (R),,P X-

Column 12, line 3, toleuenesulfonate should read toluenesulfonate.Column 13, line 22, 1979 should read 1970-". Column 16, line 33,waterinsoluble should read waterinso1uble---. Column 17, line 6,"watersoluble" should read ---water-soluble---5 line 56,"polyvin1y"should read polyvinyl---. Column 18, line 1 1, hydrozuinone" should read--hydroquinone--. Column 19, line 17 susbstantially should read--.-substantial1y---; lines 21-22, 'light-refelective" should read--light-reflective-; line 11, "capaicty" should read ---capacity--.Column 20, line 26, "3,2O L,3l3" should read ---3,206,313--; line 30, orshould read ---of---- line 17, "PAt. No. 3,726,1 T0" should read --Pat.No. 3,736,1fi0---; line 52, obtain should read --obtained---. Column 21,line 66, developoer" should read ---developer--. Column 22, line 28,"trannsfer" should read ---transfer--; line 29, modanted {liage 1 of 2pages

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT AND AT LEAST ONE LAYERTHEREON CONTAINING A PHOTOGRAHPIC SILVER HALIDE HAVING ASSOCIATEDTHEREWITH A DYE DEVELOPER WHICH IS DIFFUSIBLE IN AN ALKALINE PROCESSINGMEDIUM AND HAS THE GENERAL FORMULA:
 2. A photographic element accordingto claim 1 wherein (SID) is a group having the formula: (COUP) N-Ar-OHwherein (COUP) is a color coupler connected to the nitrogen atom at itscoupling position and Ar is an arylene group containing from 6 to 20carbon atoms.
 3. A photographic element according to claim 2 wherein Aris a phenylene group.
 4. A photographic element according to claim 1which comprises at least one layer containing an ''onium salt inwater-permeable association with said dye developer.
 5. A photographicelement according to claim 1 wherein D comprises an aromatic nucleuswhich contains at least two substituents thereon from the class ofhydroxy groups, primary amino groups or alkylamino groups.
 6. Aphotographic element according to claim 1 wherein D- is a hydroquinonegroup.
 7. A pHotographic element according to claim 1 wherein saidelement comprises at least two separate layers containing a silverhalide emulsion, each having a separate dye developer of said formulaassociated therewith.
 8. A photographic element according to claim 1wherein said element comprises a blue-sensitive silver halide emulsionlayer having associated therewith a yellow-forming indophenol dyedeveloper, a green-sensitive silver halide emulsion layer havingassociated therewith a magenta-forming indophenol dye developer, and ared-sensitive silver halide emulsion layer having associated therewith acyan-forming indophenol dye developer.
 9. A photographic elementaccording to claim 8 wherein said cyan-forming dye developer, saidmagenta-forming dye developer and said yellow-forming dye developer areeach of said formula: D-(SID) and said element contains animage-receiving layer.
 10. A photographic element according to claim 2wherein Ar is a phenylene group and said OH group is para to saidnitrogen atom.
 11. A photographic element according to claim 1 whereinsaid dye developer has the formula: D-(PYZ) N-Ar-OH wherein D- is anaromatic nucleus polysubstituted with hydroxy groups, primary aminogroups or alkylamino groups to provide a group which is capable ofdeveloping silver halide, Ar is a phenylene group, and (PYZ) is apyrazolone coupler radical or a pyrazolotriazole coupler connected atits coupling position to said nitrogen atom.
 12. A photographic elementaccording to claim 1 wherein said dye developer has the formula: D-(KMC)N-Ar-OH wherein D- is an aromatic nucleus polysubstituted with hydroxygroups, primary amino groups or alkylamino groups to provide a groupwhich is capable of developing silver halide, Ar is a phenylene group,and (KMC) is an open-chain ketomethylene coupler radical connected atits coupling position to said nitrogen atom.
 13. A photographic elementaccording to claim 1 wherein said dye developer has the formula: D-(PhC)N-Ar-OH wherein D- is an aromatic nucleus polysubstituted with hydroxygroups, primary amino groups or alkylamino groups to provide a groupwhich is capable of developing silver halide, Ar is a phenylene group,and (PhC) is a phenolic coupler radical connected at its couplingposition to said nitrogen atom.
 14. A photographic film unit comprising:a. a photosensitive element comprising a support having thereon a layercontaining a silver halide composition having associated therewith a dyedeveloper which is diffusible in an alkaline processing medium and hasthe formula: D-(SID) wherein D- is an aromatic nucleus polysubstitutedwith hydroxy groups, primary amino groups or alkylamino groups toprovide a group which is capable of developing silver halide, and (SID)is an indophenol dye moiety; b. a dye image-receiving layer; and c.means for discharging an alkaline processing composition within saidfilm unit.
 15. The film unit of claim 14 wherein said image-receivinglayer is located in said photosensitive element between said support andany said silver halide composition layer.
 16. A film unit according toclaim 14 containing an ''onium salt in liquid-permeable association withsaid dye developer and which is sequestered from said dye developeruntil contact with said liquid processing composition.
 17. The film unitof claim 14 wherein said photosensitive element comprises a supporthaving thereon: a. a red-sensitive silver halide emulsion layer havingassociated therewith a cyan-forming dye developer; b. a green-sensitivesilver halide emulsion layer having associated therewith amagenta-forming dye developer; and c. a blue-sensitive silver halideemulsion layer having associated therewith a yellow-forming dyedeveloper.
 18. A film unit according to claim 14 wherein said dyeimage-receiving layer is coated on a separate support and is adApted tobe superposed on said photosensitive element after exposure thereof. 19.A film unit according to claim 14 wherein said image-receiving layer iscoated adjacent said silver halide emulsion layers with an opaque layerbetween said silver halide emulsion layers and said image-receivinglayer.
 20. A film unit according to claim 14 wherein said dischargingmeans comprises a rupturable container and is so positioned duringprocessing of said film unit that a compressive force applied to saidcontainer by pressure-applying members will effect a discharge of thecontainer''s contents between said dye image-receiving layer and thelayer most remote from the support of said photosensitive element.
 21. Afilm unit according to claim 14 wherein said discharging means comprisesa rupturable container and is so positioned during processing of saidfilm unit that a compressive force applied to said container bypressure-applying members will effect a discharge of the container''scontents between the layer most remote from the support of saidphotosensitive element and a cover sheet superposed on saidphotosensitive element.
 22. A photographic film unit according to claim14 wherein said dye developer has the formula:
 23. A photographic filmunit according to claim 14 wherein said dye developer has the formula:24. A photographic film unit according to claim 14 wherein said dyedeveloper has the formula:
 25. A process for producing a photographictransfer image comprising: a. imagewise-exposing a photosensitiveelement comprising a support having thereon a layer containing a silverhalide composition having associated therewith a dye developer which isdiffusible in an alkaline processing medium and has the formula: D-(SID)wherein D- is an aromatic nucleus polysubstituted with hydroxy groups,amino groups or alkylamino groups to provide a group which is capable ofdeveloping silver halide, and (SID) is an indophenol dye moiety; b.treating said photosensitive element with an alkaline processingcomposition to effect development of said exposed silver halidecomposition layer; c. forming an imagewise distribution of said dyedeveloper as a function of development of said silver halide compositionlayer; d. at least a portion of said imagewise distribution ofdiffusible dye developer diffusing to an image-receiving layer; and e.contacting said dye developer with an ''onium compound at some pointafter imagewise exposure.
 26. A process according to claim 25 whereinsaid image-receiving layer contains an ''onium compound.
 27. The processof claim 25 wherein said treatment step b) is effected by: a.superposing over the layer outermost from the support of saidphotosensitive element said image-receiving layer coated on a support;b. positioning a rupturable container containing said alkalineprocessing composition between said exposed photosensitive element andsaid image-receiving layer; and c. applying a compressive force to saidcontainer to effect a discharge of the container''s contents betweensaid outermost layer of said exposed photosensitive element and saidimage-receiving layer.
 28. The process of claim 25 wherein said supportis transparent and said image-receiving layer is located between saidsupport and said silver halide composition layer, and said treatment iseffected by applying a compressive force to a rupturable containerlocated between the outermost layer of said photosensitive element and atransparent superposed cover sheet, and wherein said container containsan alkaline processing composition which is discharged by saidcompressive force.
 29. A process according to claim 25 whereindevelopment of said exposed silver halide composition layer is carriedout with an auxiliary developer present in said layer.
 30. Aphotographic product comprising a support having thereon an imagereceiving layer which contains an imagewIse distribution of an ''oniumindophenoxide of the formula: D-(SID) M wherein D- is an aromaticnucleus polysubstituted with hydroxy groups, amino groups or alkylaminogroups to provide a group which is capable of developing silver halide,(SID) is an indophenol dye moiety, and M is an ''onium group.
 31. Aphotographic product according to claim 30 wherein M is a quaternaryammonium group.
 32. A photographic product according to claim 30 whereinsaid ''onium indophenoxide has the formula: D-(COUP) N-Ar-O M wherein D-is an aromatic nucleus polysubstituted with hydroxy groups, amino groupsor alkylamino groups to provide a group which is capable of developingsilver halide, (COUP) is a photographic color coupler, Ar is an arylenegroup containing from about 6 to about 20 carbon atoms, and M is an''onium group.
 33. A photographic product according to claim 32 wherein(COUP) is an open-chain ketomethylene color coupler group connected atits coupling position to said nitrogen atom.
 34. A photographic productaccording to claim 32 wherein (COUP) is a pyrazolone or pyrazolotriazolecolor coupler group connected at its coupling position to said nitrogenatom.
 35. A photographic product according to claim 32 wherein (COUP) isa phenolic color coupler connected at its coupling position to saidnitrogen atom.
 36. A photographic product according to claim 30 whichcontains 1) an ''onium indophenoxide of said formula wherein (SID)comprises a phenolic color coupler, 2) an ''onium indophenoxide of saidformula wherein (SID) comprises an open-chain ketomethylene colorcoupler and 3) an ''onium indophenoxide of said formula wherein (SID)comprises a pyrazolone or pyrazolotriazole color coupler.
 37. Aphotographic product according to claim 30 wherein said image-receivinglayer comprises a polymer with ''onium groups thereon.
 38. Aphotographic product according to claim 30 wherein said M represents animmobile ''onium compound which is present in said image-receiving layerat concentrations of about 25 mg. to 1000 mg. per square foot.
 39. Aphotographic product according to claim 30 wherein D- is a hydroquinonegroup or an oxidized hydroquinone group.